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Controlling heat flow is a key challenge for applications ranging from thermal management in electronics to energy systems, industrial processing, and thermal therapy. However, progress has generally been limited by slow response times and low tunability in thermal conductance. In this work, we demonstrate an electronically gated solid-state thermal switch using self-assembled molecular junctions to achieve excellent performance at room temperature. In this three-terminal device, heat flow is continuously and reversibly modulated by an electric field through carefully controlled chemical bonding and charge distributions within the molecular interface. The devices have ultrahigh switching speeds above 1 megahertz, have on/off ratios in thermal conductance greater than 1300%, and can be switched more than 1 million times. We anticipate that these advances will generate opportunities in molecular engineering for thermal management systems and thermal circuit design. 

Carboranedithiol isomers adsorbing with opposite orientations of their dipoles on surfaces are self-assembled together to form mixed monolayers where both lateral dipole−dipole and lateral thiol−thiolate (S−H···S) interactions provide enhanced stability over single-component monolayers. We demonstrate the first instance of the ability to map individual isomers in a mixed monolayer using the model system carboranedithiols on Au{111}. The addition of methyl groups to one isomer provides both an enhanced dipole moment and extra apparent height for differentiation via scanning tunneling microscopy (STM). Associated computational investigations rationalize favorable interactions of mixed pairs and the associated stability changes that arise from these interactions. Both STM images and Monte Carlo simulations yield similarly structured mixed monolayers, where approximately 10% of the molecules have reversed dipole moment orientations but no direct chemical attachment to the surface, leading to homogeneous monolayers with no apparent phase separation. Deprotonating the thiols by depositing the molecules under basic conditions eliminates the lateral S−H···S interactions while accentuating the dipole− dipole forces. The molecular system investigated is composed of isomeric molecules with opposite orientations of dipoles and identical surface packing, which enables the mapping of individual molecules within the mixed monolayers and enables analyses of the contributions of the relatively weak lateral interactions to the overall stability of the assemblies.